WO2019054397A1

WO2019054397A1 - Laminate, molded article, and method for producing molded article

Info

Publication number: WO2019054397A1
Application number: PCT/JP2018/033751
Authority: WO
Inventors: 要近藤
Original assignee: 出光ユニテック株式会社
Priority date: 2017-09-12
Filing date: 2018-09-12
Publication date: 2019-03-21
Also published as: EP3683052A1; JPWO2019054397A1; US20200276796A1; EP3683052A4

Abstract

This laminate includes a thermoplastic resin layer and a protective layer, the protective layer including a welding layer, and the welding layer including a thermoplastic elastomer.

Description

LAMINATE, MOLDED BODY, AND METHOD FOR PRODUCING MOLDED BODY

The present invention relates to a laminate, a molded body, and a method of manufacturing a molded body.

In various fields such as automobiles, home appliances, building materials, daily necessities, information communication devices, etc., painting is used as a method of improving the design of the appearance. However, since the coating emits a large amount of volatile organic compounds (VOC), the environmental load is large. In addition, a large amount of energy is consumed in the control and baking process of the temperature and humidity of the paint booth, and a large amount of carbon dioxide is discharged. In particular, in the production process of automobiles, carbon dioxide emitted by painting accounts for 20% of the entire production process. In order to reduce the environmental impact associated with painting, alternatives to painting have been actively developed.

As an alternative means of painting, there is a method of coating a decorative sheet on a housing surface, and the environmental load is low compared to painting. For the decorative sheet, resins such as polypropylene, polycarbonate, acrylic resin, acrylonitrile-butadiene-styrene copolymer (hereinafter sometimes referred to as "ABS resin") are usually used.

As a decorative sheet, Patent Document 1 discloses a decorative sheet for insert molding in which a base material sheet, a printing layer, and a surface resin layer are laminated, and the base material sheet has a butadiene component ratio of 10 as a whole. Up to 33% by weight ABS resin is used.
Patent Document 2 discloses decorative molding in which a first layer made of a transparent thermoplastic resin, a second layer made of a polyolefin resin, and a third layer made of a mixed resin of an ABS resin and a polyolefin resin are laminated. A seat is disclosed.

JP 2008-94074 A Japanese Patent Application Publication No. 2003-266615 JP 2012-240421 A

As a method for obtaining the molded object covered with the decorative sheet, there is a method of integrating the decorative sheet and the resin for molding by insert molding, in-mold molding, etc. At this time, the decorative sheet and the molding are molded. It is important that the adhesive resin be in close contact with the resin.

As a method for bringing the decorative sheet and the molding resin into close contact with each other, there is a method of providing a binder closely adhering to the molding resin by screen printing, a method of bonding a resin sheet to be welded with the molding resin, and the like.
With regard to the former, the corresponding binder is present when the molding resin is polypropylene, polycarbonate or ABS resin, but there is no binder in intimate contact with the other molding resins.
In the latter case, usually, resin sheets of the same type as the molding resin are laminated and welding is performed at the time of insert molding or in-mold molding. Therefore, it is necessary to change the resin sheet in accordance with the resin for molding (for example, Patent Document 3), and there is a problem that the number of processes increases and the operation becomes complicated.

Further, among the above-described resins, polypropylene which is lightweight and excellent in chemical resistance is positively examined as a resin used for the decorative sheet. However, when a decorative sheet made of polypropylene and a molding resin such as ABS resin or polycarbonate having a high molding temperature are insert-molded or in-mold molded, design damage or insufficient adhesion occurs in the vicinity of the molding resin gate was there. As a countermeasure against this, there is a method of bonding a protective sheet of ABS resin to the decorative sheet, but when the protective sheet is used, warpage or distortion may occur in the preliminary shaped body or the injection molded body.

For example, when polypropylene is used for the resin layer of the decorative sheet in Patent Document 1 and ABS resin is used for the base sheet, warpage occurs during preliminary shaping or injection molding, and processing becomes difficult.
In regard to Patent Document 2, in general, the ABS resin and the polyolefin resin are incompatible, and it is difficult to obtain a smooth sheet even using a compatibilizer. If the sheet (third layer) is not smooth, the irregularities of the sheet (third layer) will rise on the sheet for decorative molding if preliminary shaping or injection molding is performed, and the appearance will be impaired.

Thus, there is still room for improvement in insert molding and in-mold molding using a decorative sheet, and decorative sheets (laminated bodies) to be welded to various molding resins are required. In addition, in the case of a decorative sheet containing a polyolefin (for example, polypropylene), a decorative sheet (laminated body) that is resistant to deformation such as warpage or distortion during insert molding or in-mold molding is required.

An object of the present invention is to provide a highly versatile decorative sheet (laminated body) to be welded to various molding resins.
Another object of the present invention is to provide a decorated sheet using polyolefin among the above-mentioned decorated sheets, with no or reduced deformation at the time of molding.

As a result of intensive studies conducted by the present inventor, when a layer (welding layer) containing a thermoplastic elastomer is employed as a protective layer of a decorative sheet (or as a part of a protective layer), an ABS resin used in insert molding or in-mold molding In order to obtain sufficient adhesion with molding resins such as polycarbonate, polystyrene, polyester, polyamide, acrylonitrile-styrene copolymer, acrylic resin, and polymer alloys containing two or more of these, according to the molding resin It has been found that it is possible to produce a molded article having excellent durability without changing the protective sheet.

Furthermore, when a layer (welding layer) containing a thermoplastic elastomer is adopted as a protective layer (or as a part of a protective layer) of the decorative sheet containing polyolefin among the decorative sheets, the difference in shrinkage between layers is small. As a result, it has been found that warpage and distortion during molding can be reduced, and the present invention has been completed.
According to the present invention, the following laminates and the like are provided.
1. Including a thermoplastic resin layer and a protective layer,
The protective layer comprises a weld layer,
The laminated body in which the said welding layer contains a thermoplastic elastomer.
2. The laminate according to 1, wherein the thermoplastic elastomer of the welding layer is a polyester thermoplastic elastomer.
3. The protective layer includes a base material layer on the thermoplastic resin layer side of the welding layer,
The base material layer contains one or more resins selected from the group consisting of polyolefin, polycarbonate, acrylic resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polystyrene, polyester and polyamide 1 or 2 The laminated body as described in.
4. The protective layer includes a bonding layer between the welding layer and the base layer,
The laminate according to 3, wherein the bonding layer comprises one or more resins selected from the group consisting of modified polyolefins, styrenic thermoplastic elastomers, and polyolefins.
5. The protective layer includes an anchor coat layer between the welding layer and the base layer,
The laminate according to 3, wherein the anchor coat layer comprises one or more resins selected from the group consisting of urethane resins, acrylic resins, polyolefins and polyesters.
6. The laminate according to any one of 1 to 5, wherein the welding layer further contains an acrylonitrile-butadiene-styrene copolymer.
7. The laminate according to any one of 1 to 6, wherein the thermoplastic resin layer comprises a polyolefin.
8. 7. The laminate according to 7, wherein the thermoplastic resin layer comprises polypropylene.
9. The laminate according to 8, wherein the isotactic pendart fraction of the polypropylene is 85 mol% to 99 mol%.
10. The laminate according to 8 or 9, wherein the crystallization rate of the polypropylene at 130 ° C. is 2.5 min ⁻¹ or less.
11. The laminate according to any one of 8 to 10, wherein the polypropylene contains smetic acid crystals.
12. The laminate according to any one of 8 to 11, wherein the polypropylene has an exothermic peak of 1.0 J / g or more on the low temperature side of the maximum endothermic peak in a differential scanning calorimetry curve.
13. The laminate according to any one of 7 to 12, wherein the thermoplastic resin layer does not contain a nucleating agent.
14. The thermoplastic resin layer according to any one of 1 to 6, wherein the thermoplastic resin layer comprises one or more selected from the group consisting of polycarbonate, polyamide resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and acrylic resin Stack.
15. The laminate according to any one of 1 to 14, which includes a printing layer on a part or the whole of the surface on the protective layer side of the thermoplastic resin layer.
16. One or more resins selected from the group consisting of a urethane resin, an acrylic resin, a polyolefin, and a polyester, including an easy bonding layer on a part or the whole of the surface on the protective layer side of the thermoplastic resin layer The laminate according to any one of 1 to 15, which comprises
17. The surface of the easy bonding layer opposite to the thermoplastic resin layer includes an undercoat layer containing one or more resins selected from the group consisting of urethane resin, acrylic resin, polyolefin and polyester, and the undercoat layer And a metal layer containing one or more metal elements selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum and zinc on the opposite side of the easy bonding layer. The laminated body of 16.
A molded article produced using the laminate according to any one of 18.1 to 17.
20. The laminate according to any one of 19.1 to 17, and an acrylonitrile-butadiene-styrene copolymer, a polycarbonate, a polyester, a polyamide, a polystyrene, a polystyrene, an acrylonitrile-styrene copolymer, and an acrylic resin selected from the group 1 The molded object manufactured using the above resin for shaping | molding.
20. The molded article according to 18 or 19, wherein the thermoplastic resin layer in the laminate contains polypropylene, and the isotactic pendart fraction of the polypropylene is 85 mol% to 99 mol%.
21. The molded article according to any one of 18 to 20, wherein the thermoplastic resin layer in the laminate contains polypropylene, and the crystallization rate of the polypropylene at 130 ° C. is 2.5 min ⁻¹ or less.
22. A method for producing a molded body, comprising: attaching the laminate according to any one of 22.1 to 17 to a mold and supplying a molding resin to integrate them.
23. A molded body, wherein the laminate according to any one of 23.1 to 17 is shaped to conform to a mold, the shaped laminate is attached to the mold, and a molding resin is supplied and integrated. Manufacturing method.
24. The molding resin is one or more resins selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polycarbonate, polystyrene, polyester, polyamide, acrylonitrile-styrene copolymer, and acrylic resin, as described in 22 or 23, Manufacturing method of molded articles.

According to the present invention, it is possible to provide a highly versatile decorative sheet (laminated body) welded to various molding resins. Further, according to the present invention, a decorative sheet using polyolefin among the above-described decorative sheets can be provided with no or reduced deformation at the time of molding.

1 is a schematic cross-sectional view of a laminate according to one aspect of the present invention. 1 is a schematic cross-sectional view of a laminate according to one aspect of the present invention. It is the schematic of the apparatus used by the Example and the comparative example. It is the schematic of the apparatus used by the Example and the comparative example.

[Laminate]
The laminate in one aspect of the present invention includes a thermoplastic resin layer and a protective layer. The protective layer comprises a weld layer, which comprises a thermoplastic elastomer. The layered product in one mode of the present invention can be used as a decoration sheet for giving decoration to a forming object.

The protective layer is a thermoplastic resin layer or a printed layer formed by the heat of the molten resin (molding resin) injected when the molded body is manufactured by injection molding (in-mold molding, insert molding, etc.) using a laminate. It is a layer that prevents melting.

When the protective layer contains a thermoplastic elastomer, the protective layer and the molding resin are easily heat-welded, so that it is possible to obtain a molded article with high adhesion between the laminate and the casing and excellent in durability. It becomes. The molding resin is not limited as long as it is a thermoplastic resin, and is, for example, ABS resin, polycarbonate, polystyrene, polyester, polyamide, acrylonitrile-styrene copolymer, acrylic resin, polymer alloy containing two or more of them, etc. Even if it is these, it heat-seals easily.
Further, in one aspect of the present invention, when a polyolefin is used for the thermoplastic resin layer, the shrinkage ratio of the protective layer and the polyolefin resin layer should be approximately the same because the welding layer contained in the protective layer contains a thermoplastic elastomer. Can. Thereby, deformation such as warpage distortion at the time of molding can be minimized, and the processability of the laminate can be improved.

The protective layer may have a single-layer structure consisting of a single layer, or may have a laminated structure consisting of two or more layers. When the protective layer has a single-layer structure, the protective layer is a welding layer. When the protective layer has a laminated structure, at least one of the two or more layers is a welding layer, and preferably the outermost layer of the laminated structure (the layer opposite to the thermoplastic resin layer) is a welding layer. In the laminate according to one aspect of the present invention, preferably, the layer in contact with the molding resin during molding is a welding layer.

A schematic cross-sectional view of a laminate according to one aspect of the present invention is shown in FIG.
In FIG. 1, the laminate 1 includes a thermoplastic resin layer 10 and a protective layer (welding layer) 20. FIG. 1 is merely for explaining the layer structure, and the aspect ratio and the film thickness ratio are not necessarily accurate.

Hereinafter, each layer which comprises the laminated body by one aspect of this invention is demonstrated. In the present specification, “x to y” represents a numerical range of “x or more and y or less”.

(Thermoplastic resin layer)
The thermoplastic resin layer is a resin layer containing a thermoplastic resin.
As the thermoplastic resin, polyolefin, polycarbonate, polyamide resin, ABS resin, acrylonitrile-styrene copolymer (hereinafter sometimes referred to as "AS resin"), acrylic resin, etc. can be used, and two or more of these can be used. It may be a polymer alloy (eg, polycarbonate-ABS resin alloy, polyamide-ABS resin alloy, etc.).

As polyolefin, polyethylene, polypropylene, cyclic polyolefin etc. can be used. Among these, polypropylene is preferable from the viewpoint of chemical resistance, durability and moldability.
Polypropylene is a polymer containing at least propylene. Specifically, homopolypropylene, a copolymer of propylene and olefin, and the like can be mentioned. Homopolypropylene is preferred for reasons of heat resistance and hardness.

The copolymer of propylene and olefin may be a block copolymer or a random copolymer, or a mixture thereof.
Examples of the olefin include ethylene, butylene and cycloolefin.

The polypropylene preferably has an isotactic pentad fraction of 80% by mole or more and 98% by mole or less. More preferably, it is 86 mol% or more and 98 mol% or less, more preferably 91 mol% or more and 98 mol% or less. If the isotactic pentad fraction is less than 80 mol%, the rigidity of the molded sheet may be insufficient. On the other hand, when the isotactic pentad fraction exceeds 98 mol%, the transparency of the sheet may be reduced. By being in the said range, high transparency is obtained and it becomes easy to decorate favorably.

The isotactic pentad fraction is an isotactic fraction at a pentad unit (one in which five propylene monomers are continuously isotactically bonded) in a molecular chain of a resin composition. The method of measuring this fraction is described, for example, in Macromolecules, Vol. 8 (1975) 687, and can be measured by ¹³ C-NMR.

It is preferable from the viewpoint of formability that the crystallization rate at 130 ° C. is 2.5 min ⁻¹ or less.
Crystallization rate of the polypropylene is preferably 2.5 min ^-1 or less, 2.0Min ^-1 or less is more preferable. If the crystallization rate is 2.5 min ⁻¹ or less, rapid hardening of the portion in contact with the mold can be suppressed, and a decrease in design can be prevented. The crystallization rate is measured by the method described in the examples.

The polypropylene preferably contains smetica crystals as a crystal structure. Smethica crystals are mesophases in a metastable state and are preferred because they are excellent in transparency because the size of each domain is small. Moreover, since it is in a metastable state and the sheet is softened with a low amount of heat as compared with the α crystal which has been crystallized, it is preferable because it is excellent in formability.
The polypropylene may contain other crystal forms such as β crystals, γ crystals, and amorphous parts in addition to smetica crystals. For example, 30% by mass, 50% by mass, 70% by mass or 90% by mass or more of polypropylene may be smetica crystals.

Polypropylene preferably has an exothermic peak of 1.0 J / g or more (more preferably 1.5 J / g or more) on the low temperature side of the maximum endothermic peak in a differential scanning calorimetry curve. The upper limit is not particularly limited, but is usually 10 J / g or less.
The exothermic peak is measured using a differential scanning calorimeter.

Moreover, it is preferable that the polyolefin resin layer does not contain a nucleating agent. Even when it is contained, the content of the nucleating agent in the polyolefin resin layer is 1.0% by mass or less, preferably 0.5% by mass or less.
Examples of the nucleating agent include sorbitol-based crystal nucleating agents, and examples of commercially available products include Gelol MD (Shin Nippon Chemical Co., Ltd.) and Liquemaster FC-1 (Riken Vitamin Co., Ltd.).

By setting the crystallization rate of polypropylene to 2.5 min ^-1 or less without adding a nucleating agent, and cooling at 80 ° C./sec or more to form a smetica crystal, a laminate having excellent designability can be obtained. . In addition, after shaping and heating in the production of a molded product to be described later, the polyolefin resin layer is transformed to α crystals while maintaining the fine structure derived from smetica crystals. This transfer can further improve surface hardness and transparency.

That is, in order to obtain a polypropylene excellent in transparency and gloss with an isotactic pentad fraction of 80 mol% or more and 98 mol% or less and a crystallization rate of polypropylene of 2.5 min ⁻¹ or less, a smectica is usually used. It is necessary to form crystals. In the production of a molded product to be described later, polypropylene is converted to α crystals while maintaining the fine structure derived from smetic crystals by shaping after heating, but the polypropylene in the molded product has an isotactic pentad fraction of 80% by mole If it is 98 mol% or less and the crystallization rate is 2.5 min ⁻¹ or less, it can be said that it is derived from smetica crystals.

By calculating the scattering intensity distribution and the long period by the small angle X-ray scattering analysis method, it can be judged whether the polyolefin resin layer is obtained by cooling at 80 ° C./sec or more or not. That is, it is possible to judge by the above analysis whether or not the polyolefin resin layer has a fine structure derived from smetica crystals. The measurement is performed under the following conditions.
-The X-ray generator uses ultraX 18HF (manufactured by Rigaku Corporation), and uses an imaging plate for detection of scattering.
· Light source wavelength: 0.154 nm
・ Voltage / current: 50kV / 250mA
-Irradiation time: 60 minutes-Camera length: 1.085 m
Sample thickness: Stack the sheets so as to be 1.5 to 2.0 mm. Sheets are stacked so that the film formation (MD) direction is aligned.
In order to shorten the measurement time, the sheets are stacked so as to be 1.5 to 2.0 mm. However, if the measurement time is extended, even one sheet can be measured without stacking the sheets.

The cyclic polyolefin is a polymer containing a structural unit derived from a cyclic olefin, and may be a copolymer with ethylene (cyclic polyolefin copolymer).

The melt flow rate of polypropylene (hereinafter sometimes referred to as "MFR") is preferably 0.5 to 10 g / 10 min. Within this range, the formability to a film shape or a sheet shape is excellent. The MFR of polypropylene is measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS-K7210.

The MFR of polyethylene can be 0.1 to 10 g / 10 min. Within this range, the formability to a film shape or a sheet shape is excellent. The MFR of polyethylene is measured at 190 ° C. and a load of 2.16 kg in accordance with JIS-K7210.

The MFR of the cyclic polyolefin can be 0.5 to 15 g / 10 min. The MFR of cyclic polyolefins is measured at 230 ° C. and a load of 2.16 kg according to the ISO 1133 standard.

An extrusion method etc. are mentioned as a formation method of a polyolefin resin layer.
The cooling is preferably performed at 80 ° C./sec or more until the internal temperature of the polyolefin resin layer becomes less than the crystallization temperature. Thereby, the crystal structure of a polyolefin resin layer (especially polypropylene) can be made into the above-mentioned Smethica crystal. The cooling is more preferably 90 ° C./second or more, and still more preferably 150 ° C./second or more.

The polyolefin may be blended with additives such as a pigment, an antioxidant, a stabilizer, and an ultraviolet light absorber, as necessary.
Further, a modified product obtained by modifying a polyolefin with a modifying compound such as, for example, maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate and the like You may mix | blend polyolefin resin.

The polycarbonate is not particularly limited in its production method, and those produced by various known methods can be used. For example, one prepared by solution method (interfacial polycondensation method) or melting method (ester exchange method) of dihydric phenol and carbonate precursor, ie, reaction of dihydric phenol with phosgene in the presence of a terminator. What is manufactured by making it react by the transesterification method of dihydric phenol, a diphenyl carbonate, etc. in presence of the interfacial polycondensation method to make or the end terminator, etc. can be used.

Examples of dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) Sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone and the like can be mentioned. Besides this, hydroquinone, resorcin and catechol can also be mentioned. Each of these may be used alone or in combination of two or more. Among them, bis (hydroxyphenyl) alkanes are preferred, and bisphenol A is particularly preferred.

The carbonate precursor is, for example, a carbonyl halide, a carbonyl ester, or a haloformate, and specifically, phosgene, a dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like. The polycarbonate may have a branched structure, and as a branching agent, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ′ ′-tris (4-hydroxy) Phenyl) -1,3,5-triisopropylbenzene, fluoroglycine, trimellitic acid and isatin bis (o-cresol).

The viscosity average molecular weight (Mv) of the polycarbonate is usually 10,000 to 50,000, preferably 13,000 to 35,000, and more preferably 15,000 to 20,000. The viscosity average molecular weight (Mv) is obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, determining the intrinsic viscosity [η], and calculating the viscosity according to the following equation.
[Η] = 1.23 × 10 ^-5 Mv ^0.83

The molecular terminal group in polycarbonate is not particularly limited, and may be a group derived from a monovalent phenol which is a conventionally known terminator, but is derived from a monovalent phenol having an alkyl group having 10 to 35 carbon atoms. Is preferably a group of If the molecular terminal is a group derived from phenol having an alkyl group having 10 or more carbon atoms, the obtained polycarbonate composition has good fluidity, and a group derived from phenol having an alkyl group having 35 or less carbon atoms If so, the resulting polycarbonate composition has good heat resistance and impact resistance.
Examples of the monovalent phenol having an alkyl group having 10 to 35 carbon atoms include decylphenol, undecylphenol, dodecylphenol, tridecylphenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, heptadecylphenol and octadecylphenol And nonadecylphenol, icosylphenol, docosylphenol, tetracosylphenol, hexacosylphenol, octacosylphenol, triacontylphenol, dotriacontylphenol, pentatriacontylphenol and the like.

The alkyl group of these alkylphenols may be any position of o-, m- and p- with respect to the hydroxyl group, but the position of p- is preferred. The alkyl group may be linear, branched or a mixture thereof. As this substituent, at least one of them may be an alkyl group having a carbon number of 10 to 35, and the other four are not particularly limited, and an alkyl group having a carbon number of 1 to 9 and a carbon number of 6 to 20 It may be an aryl group, a halogen atom or unsubstituted.
The end capping with a monovalent phenol having an alkyl group having a carbon number of 10 to 35 may be either one end or both ends, and the end modification ratio is an aspect of high fluidization of the obtained PC resin composition Therefore, the content is preferably 20% or more, more preferably 50% or more, with respect to all the ends. That is, the other end may be a hydroxyl end, or an end that is sealed using the following other end terminator.

Other terminal stoppers include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, p-tert commonly used in the production of polycarbonate resins. -Amylphenol, bromophenol and tribromophenol, pentabromophenol etc. may be mentioned. Among them, compounds which do not contain halogen are preferable in view of environmental problems.
Polycarbonate is a polyester-polycarbonate obtained by polymerizing polycarbonate in the presence of an ester precursor such as a PC-POS copolymer, a difunctional carboxylic acid such as terephthalic acid, or an ester-forming derivative thereof besides polycarbonate. Copolymers such as resins or other polycarbonate resins may be suitably contained.

Polycarbonate is preferably melt volume flow rate (MVR) is 1 ~ 50cm ^3/10 minutes as measured by JIS K7210.

Examples of the polyamide resin include polyamide 66, polyamide 6, polyamide 1010, polyamide 12, polyamide 11 and the like.
The polyamide resin preferably has an MFR of 0.5 to 50 g / 10 min as measured according to JIS K7210.

The ABS resin is not particularly limited, but may contain structural units derived from monomers other than acrylonitrile, butadiene and styrene.
The ABS resin preferably has a MFR of 0.5 to 50 g / 10 min as measured according to JIS K7210.

The AS resin is not particularly limited, but may contain structural units derived from monomers other than acrylonitrile and styrene.
The AS resin preferably has a MFR of 0.5 to 50 g / 10 min as measured according to JIS K 7210.

The acrylic resin preferably has a MFR of 1 to 50 g / 10 min as measured according to JIS K7210.

The polycarbonate-ABS resin alloy is a resin obtained by mixing the polycarbonate and the ABS resin in a molten state.
The polycarbonate-ABS resin alloy resin preferably has an MFR of 1 to 50 g / 10 min as measured according to JIS K7210.

The polyamide-ABS resin alloy is a resin in which the polycarbonate and the polyamide are mixed in a molten state.
The polyamide-ABS resin alloy resin preferably has an MFR of 1 to 50 g / 10 min as measured according to JIS K7210.

The thickness of the thermoplastic resin layer is usually 10 to 1000 μm, and may be 15 to 500 μm, 20 to 500 μm, or 30 to 300 μm.
The thermoplastic resin layer may use the above-described materials singly or in combination of two or more. Moreover, resin other than the resin mentioned above may be included.

(Protective layer)
The protective layer includes at least a welding layer, and may be a laminated structure including other layers such as a base layer, an anchor coat layer, and a bonding layer. In the case of the laminated structure, preferably, the outermost layer of the laminated structure, that is, the layer opposite to the thermoplastic resin layer is a welding layer.

The following configurations can be given as an example of the layered configuration of the laminate in one embodiment of the present invention.
[Thermoplastic resin layer / welding layer]
[Thermoplastic resin layer / substrate layer / welding layer]
[Thermoplastic resin layer / substrate layer / bonding layer / welding layer]
[Thermoplastic resin layer / substrate layer / anchor coat layer / welding layer]
"/" Indicates that the layers are stacked.

A schematic cross-sectional view of a laminate in the case where the protective layer has a laminated structure including a base material layer, a bonding layer, and a welding layer is shown in FIG.
In FIG. 2, the laminate 2 includes the thermoplastic resin layer 10 and the protective layer 20, and the protective layer 20 includes the base layer 22, the bonding layer 24 and the welding layer 26 in order from the thermoplastic resin layer 10 side. It is a laminated structure. FIG. 2 is merely for explaining the layer structure, and the aspect ratio and the film thickness ratio are not necessarily accurate.
Hereinafter, each layer which comprises a protective layer is demonstrated.

(Welding layer of protective layer)
The welding layer comprises a thermoplastic elastomer.
Thermoplastic elastomers are usually composed of hard segments and soft segments. Thermoplastic elastomers exhibit thermoplasticity because the hard segment exhibits rubber elasticity because the hard segment fixes the flow of molecular chains at normal temperature, and the hard segment plasticizes at the temperature where the hard segment melts to release the molecular chain fixation. .
The presence of the soft segment makes it possible to make the shrinkage of the protective layer approximately the same as the shrinkage of the thermoplastic resin layer.

Thermoplastic elastomers are generally of copolymerization type in which hard segments and soft segments are connected by copolymerization, and dispersion type of sea-island structure in which hard segments constitute matrix and soft segments constitute domains.

Examples of the thermoplastic elastomer used in one aspect of the present invention include polyester thermoplastic elastomers and acrylic thermoplastic elastomers, and polyester thermoplastic elastomers are preferable.

The polyester-based thermoplastic elastomer is an elastomer in which polyester is used as a hard segment and a rubber component is used as a soft segment.
Examples of the hard segment polyester include polyethylene terephthalate and polybutylene terephthalate, and polybutylene terephthalate is preferable. Examples of the rubber component of the soft segment include polyether, polycarbonate and the like, and polyether is preferable.

The polyester-based thermoplastic elastomer may be of copolymerization type or of dispersion type.

The MFR of the polyester thermoplastic elastomer is preferably 1 to 100 g / 10 minutes, more preferably 1 to 50 g / 10 minutes. MFR is measured at 230 ° C. under a load of 21N.

The acrylic thermoplastic elastomer is an elastomer in which an acrylic resin is used as a hard segment and a rubber component is used as a soft segment.
As a hard segment acrylic resin, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, Myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like can be mentioned, with preference given to methyl methacrylate. Examples of the rubber component of the soft segment include n-butyl polyacrylate, polybutadiene, polyisoprene and the like, and n-butyl polyacrylate is preferable.
The acrylic thermoplastic elastomer may be of copolymerization type or of dispersion type.

The MFR of the acrylic thermoplastic elastomer is preferably 2 to 100 g / 10 min. MFR is measured at 230 ° C. and a load of 2.16 kg in accordance with ISO 1133.

The welding layer may contain an ABS resin in addition to the thermoplastic elastomer. By containing the ABS resin, the rigidity of the welding layer can be improved. The content of the ABS resin is preferably 30% by mass or less, more preferably 5 to 30% by mass. Within this range, the shrinkage rate of the protective layer can be kept good, and the rigidity can be enhanced.

The ABS resin is as described for the thermoplastic resin layer. Also, instead of the ABS resin, an acrylonitrile-styrene copolymer (AS resin) not containing a structural unit derived from butadiene may be used.

For example, 30 mass% or more, 50 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.9 mass% or more, or 100 mass% of the welding layer % May be a thermoplastic elastomer, or a thermoplastic elastomer and an ABS resin. The welding layer may consist essentially of a thermoplastic elastomer, or a thermoplastic elastomer and an ABS resin.

The thickness of the welding layer is preferably 5 to 300 μm, more preferably 10 to 250 μm, and may be 10 to 200 μm, 10 to 150 μm, or 50 to 150 μm.

(Base layer of protective layer)
The substrate layer is preferably a layer containing one or more resins selected from the group consisting of polyolefins, polycarbonates, acrylic resins, ABS resins, AS resins, polystyrenes, polyesters, and polyamides. The substrate layer preferably comprises one or more resins selected from the group consisting of polyolefins, polycarbonates, ABS resins, AS resins and polyamides.

By providing the base material layer, the rigidity of the entire protective layer can be improved as compared with the case of only the welding layer, so that the laminated body has stiffness and handling at the time of processing becomes easy.

The polyolefin, polycarbonate, acrylic resin, ABS resin, AS resin and polyamide are as described for the thermoplastic resin layer.

As polystyrene, polystyrene alone or polystyrene may contain a rubber component. The polystyrene preferably has an MFR measured according to JIS K 7210, and is 1 to 50 g / 10 min.

The polyester resin preferably has a MFR of 1 to 50 g / 10 min as measured according to JIS K7210.

The thickness of the substrate layer is preferably 20 to 500 μm, more preferably 20 to 300 μm.

For example, 30 mass% or more, 50 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.9 mass% or more of the base material layer The mass% may be the above-described resin.

(Bonding layer of protective layer)
The bonding layer is preferably a layer containing one or more resins selected from the group consisting of modified polyolefins, styrenic thermoplastic elastomers, and polyolefins.

The raw material polyolefin of said polyolefin and modified polyolefin is as having demonstrated by the thermoplastic resin layer, and a polypropylene is preferable.

Examples of the modifying compound for polyolefin include maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate and methyl methacrylate.

Styrene-based thermoplastic elastomers include styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isoprene-butadiene Rubber block copolymers containing styrene block such as block copolymer (SIB), styrene-isoprene block copolymer (SI), styrene-ethylene-propylene block copolymer (SEP) and their hydrogenated products Can be mentioned.

The MFR of the styrene-based thermoplastic elastomer is preferably 1 to 20 g / 10 min. MFR is measured at 230 ° C. and a load of 2.16 kg in accordance with ISO 1133.

The bonding layer may contain two or more of the components described above, and may be, for example, a mixed layer of a styrene-based thermoplastic elastomer (eg, 30 to 90% by mass) and a polyolefin (eg, 10 to 70% by mass).

For example, 30 mass% or more, 50 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.9 mass% or more, or 100 mass% of the bonding layer % May be the above-mentioned resin.

The thickness of the bonding layer is preferably 1 to 50 μm.

(Anchor coat layer of protective layer)
The anchor coat layer is preferably a layer containing one or more resins selected from the group consisting of urethane resins, acrylic resins, polyolefins and polyesters. In consideration of the adhesion to the base material layer and the welding layer, urethane resins and polyolefins are preferred.

The urethane resin is usually obtained by reacting at least a diisocyanate, a high molecular weight polyol and a chain extender. The high molecular weight polyol may be a polyether polyol, a polycarbonate polyol or a polyester polyol.
The anchor coat layer may be used singly or in combination of two or more of the materials described above.

For example, 30 mass% or more, 50 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 98 mass% or more, 99 mass% or more, 99.9 mass% or more of the anchor coat layer The mass% may be the above-described resin.

The anchor coat layer can be formed, for example, by applying the above-mentioned resin with a gravure coater, a kiss coater, a bar coater or the like and drying at 40 to 100 ° C. for 10 seconds to 10 minutes.

The thickness of the anchor coat layer may be 35 nm or more and 3000 nm or less, may be 50 nm or more and 2000 nm or less, and may be 50 nm or more and 1000 nm or less. If the thickness of the anchor coat layer is 35 nm or more, adhesion to other layers is sufficiently high. When the thickness of the anchor coat layer is 3000 nm or less, the occurrence of blocking due to stickiness can be suppressed.

For example, when the anchor coat layer is provided on one side of the base material layer, the adhesion to the welding layer can be improved at the time of extrusion lamination.

The protective layer may include, for example, a colored layer, a release layer, and the like in addition to the above layers.

The total thickness of the protective layer is usually 10 to 1000 μm, preferably 50 to 500 μm, and more preferably 100 to 400 μm. If the thickness of the protective layer is 10 μm or more, the surface layer can be protected from the heat of the injection resin without any problem, and design damage and adhesion failure can be suppressed. If the thickness of the protective layer is 1000 μm or less, the moldability of the laminate is excellent.

(Method of manufacturing laminate)
Although the manufacturing method in particular of the layered product concerning one mode of the present invention is not restrict | limited, For example, it can manufacture by laminating | stacking a thermoplastic resin layer and a protective layer by methods, such as dry lamination, extrusion lamination, thermal lamination. Dry lamination is preferred because the amount of heat applied to the thermoplastic resin layer during lamination is small.

(Printed layer)
The laminate according to one aspect of the present invention may include a print layer on the surface on the protective layer side of the thermoplastic resin layer. The print layer may be provided on part or all of the surface on the protective layer side of the thermoplastic resin layer.
Although it does not restrict | limit especially as a shape of a printing layer, For example, various shapes, such as a solid form, carbon tone, and a woodgrain, are mentioned.
As a printing method, a general printing method such as a screen printing method, an offset printing method, a gravure printing method, a roll coating method, a spray coating method can be used. In particular, since the film thickness of the ink can be thickened by the screen printing method, ink breakage is less likely to occur when it is formed into a complicated shape.
For example, in the case of screen printing, an ink excellent in elongation at the time of molding is preferable, and “FM3107 high concentration white” or “SIM3207 high concentration white” manufactured by Tojo Chemical Co., Ltd. can be exemplified, but not limited thereto.

(Easy bonding layer)
The laminate according to one aspect of the present invention may be provided with an easy bonding layer on part or the whole of the surface on the protective layer side of the thermoplastic resin layer. The easy bonding layer is a layer capable of enhancing the adhesion between the thermoplastic resin layer and the protective layer or an undercoat layer described later.

As a material which forms an easily bonding layer, urethane resin, acrylic resin, polyolefin resin, polyester resin etc. are mentioned. In view of adhesion to other layers and moldability, urethane resins are preferred.
The urethane resin is usually obtained by reacting at least a diisocyanate, a high molecular weight polyol and a chain extender. The high molecular weight polyol may be a polyether polyol or a polycarbonate polyol.
The easy bonding layer may use the above-described materials singly or in combination of two or more.

By providing the easily bonding layer, even when the laminate is formed into a complicated nonplanar shape, the easily bonding layer can form a layer configuration favorably following the thermoplastic resin layer.

The easy bonding layer can be formed, for example, by applying the above-described resin with a gravure coater, a kiss coater, a bar coater or the like and drying it at 40 to 100 ° C. for 10 seconds to 10 minutes.

The thickness of the easy bonding layer may be 35 nm or more and 3000 nm or less, may be 50 nm or more and 2000 nm or less, and may be 50 nm or more and 1000 nm or less. If the thickness of the easy bonding layer is 35 nm or more, the adhesion to other layers is sufficiently high. When the thickness of the easy bonding layer is 3000 nm or less, the occurrence of blocking due to stickiness can be suppressed.

On the easily bonding layer (opposite to the thermoplastic resin layer), various coatings such as an ink, a hard coat, an antireflective coat, and a thermal barrier coat can be laminated.

Further, another easy bonding layer may be provided on the surface of the thermoplastic resin layer opposite to the above-mentioned easy bonding layer (first easy bonding layer) (second easy bonding layer). By doing this, the thermoplastic resin layer can be provided with functionality such as surface treatment and hard coating.

(Undercoat layer)
The laminate according to one aspect of the present invention may be provided with an undercoat layer.
The undercoat layer is a layer capable of bringing the easily bonding layer into close contact with the metal layer described later.
As a material which forms an undercoat layer, a urethane resin, an acrylic resin, polyolefin, polyester etc. are mentioned.
An acrylic resin is preferable from the viewpoint of the whitening resistance (the difficulty in causing the whitening phenomenon) during molding and the adhesion to the metal layer. For example, “DA-105” manufactured by Arakawa Chemical Industries, Ltd. can be used.
The above materials may be used alone or in combination of two or more.

As a method of forming the undercoat layer, for example, the above-described material is applied by a gravure coater, a kiss coater, a bar coater or the like, dried at 50 to 100 ° C. for 10 seconds to 10 minutes, and at 40 to 100 ° C. It can be formed by time aging.
The thickness of the undercoat layer may be 0.05 μm to 50 μm, 0.1 μm to 10 μm, or 0.5 μm to 5 μm.

(Metal layer)
The laminate according to one aspect of the present invention may be provided with a metal layer. The metal layer is a layer containing metal or metal oxide.
The metal for forming the metal layer is not particularly limited as long as it is a metal capable of giving a metallic design to the laminate, and examples thereof include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum and zinc. It is possible to use an alloy that includes at least one of these.

Among the above, indium and aluminum and chromium are preferable because they are particularly excellent in extensibility and color tone. When the metal layer is excellent in extensibility, cracking is unlikely to occur when the laminate is three-dimensionally formed.

The method for forming the metal layer is not particularly limited, but from the viewpoint of imparting to the laminate a metallic texture having high texture and high quality, for example, vacuum evaporation, sputtering, ion plating using the above-mentioned metals A vapor deposition method such as a method can be used. In particular, the vacuum deposition method is low in cost and can reduce damage to the deposition target. The conditions of the vacuum deposition method may be appropriately set according to the melting temperature or evaporation temperature of the metal to be used.
Other than the above method, a method of applying a paste containing the above metal or metal oxide, a plating method using the above metal, or the like can also be used.

The thickness of the metal layer may be 5 nm or more and 80 nm or less. If it is 5 nm or more, the desired metallic gloss can be obtained without any problem, and if it is 80 nm or less, cracking hardly occurs.

[Molded body]
A molded object can be manufactured using the laminated body mentioned above.

In the molded article of the present invention, when the thermoplastic resin layer contains polypropylene, the isotactic pendat fraction of polypropylene is preferably 80 mol% or more and 98 mol% or less.
Further, the crystallization rate at 130 ° C. of the polypropylene preferable to be 2.5 min ^-1 or less, 2.0Min ^-1 or less is more preferable.
Even after forming into a molded body, it is possible to specify a portion corresponding to the thermoplastic resin layer of the laminate by using a phase microscope or the like. The method of measuring the isotactic pendart fraction and the crystallization rate is as described above.

[Method for producing molded body]
Examples of the method for producing a molded article according to one aspect of the present invention include in-mold molding, insert molding, coating molding and the like.

In-mold molding is a method in which a laminate is placed in a mold and molded into a desired shape by the pressure of a molding resin supplied into the mold to obtain a molded body.
As in-mold molding, it is preferable to mount the laminate on a mold and supply molding resin for integration.

In insert molding, a shaped body to be placed in a mold is pre-shaped, and a molding resin is filled in the shape to obtain a molded body. More complex shapes can be formed.
As the insert molding, the laminate may be shaped so as to conform to the mold, and the shaped laminate may be mounted on the mold, and a molding resin may be supplied and integrated.
The shaping (preliminary shaping) performed to conform to the mold can be performed by vacuum forming, pressure forming, vacuum pressure forming, press forming, plug assist forming, or the like.

As the molding resin, a moldable thermoplastic resin can be used. Specifically, polypropylene, polyethylene, polycarbonate, ABS resin, acrylic polymer, polystyrene, polyester, polyamide and the like can be exemplified, and any of them can be easily welded to the above-mentioned laminate (decorative sheet). The molding resin is not limited to the one described above.

The molding resin is preferably polycarbonate, an ABS resin, or an acrylic polymer, and more preferably polycarbonate and an ABS resin, from the viewpoint of molding temperature, appearance of the molded product, dimensional stability, and difficulty in generating sink marks in the molded product. The ABS resin is the same as that used in the welding layer described above. It may be a mixture of two or more of the above resins. Moreover, you may add inorganic fillers, such as a fiber and a talc, to resin for shaping | molding.

The supply of the molding resin is preferably performed by injection, and the pressure is preferably 5 MPa or more and 300 MPa or less. The mold temperature is preferably 20 ° C. or more and 90 ° C. or less.

[Uses such as moldings]
The laminate and the molded article according to one aspect of the present invention can be used as an interior material, an exterior material, a housing of a home appliance, a decorative steel plate, a decorative board, a housing equipment, a housing of an information communication device, etc.

The components used in Examples and Comparative Examples are shown below.
・ Polypropylene 1: Homopolypropylene, Prime Polymer Co., Ltd. “Prime Polypro F133A”, MFR: 3 g / 10 min. Polypropylene 2: Homopolypropylene, Co., Ltd. Prime Polymer “Prime Polypro F-300 SP”, MFR: 3 g / 10 min・ Polypropylene 3: random polypropylene (propylene-ethylene copolymer), Prime Polymer Co., Ltd. “Prime Polypro F 794 NV”, MFR: 5.8 g / 10 min. Polypropylene 4: Homopolypropylene, Inc. Prime Polymer Co. “Prime Polypro F -704 NP ", MFR: 7 g / 10 min. Polyester thermoplastic elastomer 1:" Tifa block A1700 N "manufactured by Mitsubishi Chemical Corporation, hard segment: polybutylene terephthalate, SO To segment: Polyether, MFR: 43 g / 10 min. Polyester thermoplastic elastomer 2: Tifa block C1701N manufactured by Mitsubishi Chemical Co., Ltd. Hard segment: Polybutylene terephthalate, soft segment: Polyether, MFR: 3 g / 10 min Maleic acid-modified polypropylene 1: "Modic F 534A" manufactured by Mitsubishi Chemical Co., Ltd. MFR: 3.5 g / 10 minutes Maleic-modified polypropylene 2: macroc F 502 manufactured by Mitsubishi Chemical Co., MFR: 1.0 g / 10 min Maleic acid-modified polypropylene 3: Modic F508, manufactured by Mitsubishi Chemical Co., Ltd. MFR: 0.8 g / 10 min Styrene thermoplastic elastomer 1: Kuraray Co., Ltd. Hybler 7311, hard segment: polystyrene Soft Segment: hydrogenated poly (isoprene / butadiene), MFR: 2 g / 10 min · ABS Resin 1: acrylonitrile - butadiene - styrene copolymer, manufactured by Asahi Kasei Chemicals Corporation, "Stylac 220P"
Polycarbonate 1: manufactured by Idemitsu Kosan Co., Ltd. "TARFLON A1900", MVR: 19cm ^3/10 minutes · AS Resin 1: acrylonitrile - styrene copolymer, manufactured by Toray Industries, Inc. "Toyolac A20C-300", MFR: 26 g / 10 min・ Polycarbonate-ABS resin alloy 1: Polymer alloy of acrylonitrile-styrene copolymer and polycarbonate, Toray Industries, Inc. “Toyolac PX10-X06”, MFR: 15 g / 10 min. Polyamide-ABS resin alloy 1: Acrylonitrile-styrene co-weight Polymer alloy of united and polyamide, Toray Co., Ltd. "Toyolac SX01", MFR: 22 g / 10 min. Anchor coat 1: polyester-based urethane resin, Toyo Moreton Co., Ltd. "Ad coat AD-335 AE"
・ Anchor coat 2: Polyether-based urethane resin, DIC Corporation "Hydran WLS-202"
・ Anchor coat 3: Polypropylene resin, "Arrow base DB-4010" made by Unitika Co., Ltd.

Example 1
[Production of laminate]
(1) Production of Thermoplastic Resin Layer A polycarbonate sheet (thermoplastic resin layer) having a thickness of 200 μm was produced using the production apparatus shown in FIG. 4 under the production conditions shown below. In the manufacturing apparatus, the molten resin extruded from the T-die 72 of the extruder is closely adhered to the cooling roll 76 by the air knife 74 and cooled by the cooling rolls 76 and 78 to form the resin sheet 71.
[Manufacturing conditions]
・ Composition: Polycarbonate 1 (100% by mass)
· Diameter of extruder: 30 mm
・ T-die 72 width: 350 mm
Take-up speed of resin sheet 71: 2.1 m / min Surface temperature of cooling rolls 76 and 78: 30 ° C.

(2) Production of Protective Layer A resin sheet (protective layer: welding layer) having a thickness of 200 μm was produced using the production apparatus shown in FIG. 4 under the production conditions shown below.
[Manufacturing conditions]
・ Formulation of protective layer: Polyester-based thermoplastic elastomer 1 (100% by mass)
· Diameter of extruder: 30 mm
・ T-die 72 width: 350 mm
Take-up speed of resin sheet 71: 2.1 m / min Surface temperature of cooling rolls 76 and 78: 30 ° C.

(3) Production of Laminate The whole of the thermoplastic resin layer obtained in (1) was screened using "POS-911 black ink" manufactured by Teikoku Ink Mfg. Co., Ltd. using T-250 mesh (polyester mesh). A solid printing layer is provided by printing and drying in a drying oven at 60 ° C. for 90 minutes, and after drying, a pressure-sensitive adhesive sheet (“mold fit 50” manufactured by Niei Kako Co., Ltd.) is laminated, and (2) The protective layers obtained in the above were laminated to obtain a laminate 1.

[Production and evaluation of molded articles]
The laminate 1 was thermoformed by vacuum pressure forming using a vacuum pressure forming machine ("FM-3M / H" manufactured by Minos Corporation) to produce a formed body 1. The top surface of the molded body 1 is a flat inverted dish shape (convex shape), and is substantially rectangular (short side 72 mm, long side 160 mm) as viewed from above, and its four corners are curved (R = 10 mm) And the height is 13 mm. The thickness of the molded body 1 is 3 mm throughout. Moreover, the part which transfers to the top | upper surface from the slope of a reverse dish shape (convex shape) shape is curvilinear shape (R = 10 mm).

The molded body 1 is mounted on a mold in which the molded body 1 fits without gaps, and the ABS resin 1 is supplied into the mold and integrated by a hydraulic injection molding machine (“IS-80 EPN” manufactured by Toshiba Machine Co., Ltd.) The molded body 2 was manufactured.

(Design damage)
The proximity | contact part in the molded object 2 with the gate of a hydraulic-type injection molding machine was observed visually, and the presence or absence of the design damage in the said part was evaluated along the following reference | standard. The results are shown in Table 1.
No damage to the design: ○
Damage to design: x

(Adhesive strength)
The laminated body 1 which comprises the molded object 2 was peeled 180 degrees by 15 mm width from supply resin (ABS resin 1), and the peeling strength of the laminated body 1 and supply resin was measured by the push pull gauge. The results are shown in Table 1.

Example 2
The protective layer was manufactured on the following conditions using the manufacturing apparatus shown in FIG. 4, and it was set as the 2 layer structure (200 micrometers in thickness) of (base material layer / welding layer).
[Manufacturing conditions]
・ Composition of base material layer: Polycarbonate 1 (100% by mass)
・ Composition of welding layer: Polyester thermoplastic elastomer 1 (100% by mass)
· Diameter of extruder for base layer: 30 mm
· Diameter of extruder of welding layer: 30 mm
・ T-die 72 width: 350 mm
Take-up speed of laminated sheet (resin sheet 71): 2.1 m / min Surface temperature of cooling rolls 76 and 78: 80 ° C.
・ Thickness of base layer: 99 μm
· Thickness of welding layer: 101 μm

Except for the above, laminates and molded articles were manufactured and evaluated in the same manner as in Example 1. The base material layer is a layer by the side of a thermoplastic resin layer among the said laminated structure. The results are shown in Table 1.

Example 3
A laminate and a molding were carried out in the same manner as in Example 2 except that the material of the thermoplastic resin layer was AS resin 1 (100% by mass) and the material of the base layer of the protective layer was AS resin 1 (100% by mass). The body was manufactured and evaluated. The results are shown in Table 1.

Example 4
The same as Example 2 except that the material of the thermoplastic resin layer is polycarbonate-ABS resin alloy 1 (100% by mass) and the material of the base layer of the protective layer is polycarbonate-ABS resin alloy 1 (100% by mass). Laminates and compacts were produced and evaluated by the method. The results are shown in Table 1.

Example 5
Same as Example 2 except that the material of the thermoplastic resin layer is polyamide-ABS resin alloy 1 (100 mass%) and the material of the base layer of the protective layer is polyamide-ABS resin alloy 1 (100 mass%) Laminates and compacts were produced and evaluated by the method. The results are shown in Table 1.

Example 6
A laminate was produced in the same manner as in Example 2. The evaluation was performed in the same manner as in Example 2 except that polycarbonate 1 was supplied instead of the ABS resin 1 in the production of the molded body 2. The results are shown in Table 1.

Example 7
A laminate was produced in the same manner as in Example 2. Evaluation was carried out in the same manner as in Example 2 except that polyamide-ABS resin alloy 1 was supplied instead of ABS resin 1 in the production of molded body 2. The results are shown in Table 1.

Comparative Example 1
A laminate and a molded body were produced and evaluated in the same manner as in Example 1 except that the material of the protective layer (welding layer) was changed to polycarbonate 1 (100% by mass). The results are shown in Table 1.

Example 8
[Production of laminate]
(1) Production of Thermoplastic Resin Layer A polypropylene sheet (thermoplastic resin layer) 51 was produced using the production apparatus shown in FIG.
The operation of the device will be described. The molten resin (polypropylene 1) extruded from the T die 52 of the extruder is sandwiched between the metal endless belt 57 and the fourth cooling roll 56 on the first cooling roll 53. In this state, the molten resin is pressure-welded by the first and fourth cooling rolls 53 and 56 and rapidly cooled. Subsequently, the polypropylene sheet is sandwiched between the metal endless belt 57 and the fourth cooling roll 56 at a circular arc portion corresponding to the lower half of the fourth cooling roll 56 and is planarly pressure-welded. After surface pressure welding and cooling by the fourth cooling roll 56, the polypropylene sheet in close contact with the metal endless belt 57 is moved onto the second cooling roll 54 as the metal endless belt 57 pivots. As described above, the polypropylene sheet is pressure-welded by the metal endless belt 57 at the arc portion corresponding to the substantially upper half circumference of the second cooling roll 54, and is cooled again. The polypropylene sheet cooled on the second cooling roll 54 is then peeled off the metal endless belt 57. The surface of the first and second cooling rolls 53 and 54 is coated with an elastic material 62 made of nitrile butadiene rubber (NBR).

The manufacturing conditions of the polypropylene sheet 51 are as follows.
· Diameter of extruder: 150 mm
・ T-die 52 width: 1400 mm
・ The thickness of polypropylene sheet 51: 200 μm
Take-up speed of polypropylene sheet 51: 25 m / min Surface temperature of fourth cooling roll 56 and metal endless belt 57: 17 ° C.
・ Cooling speed: 10,800 ° C / minute (180 ° C / second)
・ Nucleator: None

The crystallization rate of the polypropylene used for the thermoplastic resin layer was measured using a differential scanning calorimeter (DSC) ("Diamond DSC" manufactured by Perkin Elmer). Specifically, the temperature of the polypropylene is raised from 50 ° C. to 230 ° C. at 10 ° C./min, held for 5 minutes at 230 ° C., cooled from 230 ° C. to 130 ° C. at 80 ° C./min, and then to 130 ° C. It hold | maintained and performed crystallization. The measurement of the heat quantity change was started when the temperature reached 130 ° C., and a DSC curve was obtained. From the obtained DSC curve, the crystallization rate was determined by the following procedures (i) to (iv).
(I) A baseline was obtained by approximating a change in heat quantity from a point 10 times to a point 20 times from the start of the measurement to the peak top by a straight line.
(Ii) The intersection point of a tangent having a slope at the inflection point of the peak and the baseline was determined to determine the crystallization start and end times.
(Iii) From the crystallization start time obtained, the time to the peak top was measured as the crystallization time.
(Iv) The crystallization rate was determined from the reciprocal of the obtained crystallization time.
The crystallization rate of polypropylene used for the thermoplastic resin layer was 0.9 min ^-1 .

(3) Production of Laminate The whole of the thermoplastic resin layer obtained in (1) was screened using "POS-911 black ink" manufactured by Teikoku Ink Mfg. Co., Ltd. using T-250 mesh (polyester mesh). A solid printing layer is provided by printing and drying in a drying oven at 60 ° C. for 90 minutes, and the adhesive after drying has a thickness of 1.2 μm ("Unistol H200" manufactured by Mitsui Chemicals, Inc.) Were coated with a bar coater, dried at 80.degree. C. for 3 minutes, and the protective layer obtained in (2) was laminated thereon to obtain a laminate.

Using the obtained laminate, a molded body was produced and evaluated in the same manner as in Example 1. Further, the appearance of the molded body was evaluated as follows. The results are shown in Table 2.
(appearance)
The appearance of the molded body 1 was visually confirmed and evaluated in accordance with the following criteria. The results are shown in Table 1.
No warpage and distortion: ○
At least one of warp and strain is seen: x

Example 9
The protective layer was manufactured on the following conditions using the manufacturing apparatus shown in FIG. 4, and it was set as 3 layer structure (200 micrometers in thickness) of (base material layer / joining layer / welding layer).
[Manufacturing conditions]
・ Composition of base material layer: Polypropylene 2 (100 mass%)
・ Composition of bonding layer: Maleic acid modified polypropylene 1 (100% by mass)
・ Composition of welding layer: Polyester thermoplastic elastomer 1 (100% by mass)
· Diameter of extruder for base layer: 30 mm
· Diameter of bonding layer extruder: 20 mm
· Diameter of extruder of welding layer: 30 mm
・ T-die 72 width: 350 mm
Take-up speed of laminated sheet (resin sheet 71): 2.1 m / min Surface temperature of cooling rolls 76 and 78: 30 ° C.
・ Thickness of base layer: 104 μm
Bonding layer thickness: 13 μm
· Thickness of welding layer: 100 μm

Except for the above, laminates and molded articles were produced and evaluated in the same manner as in Example 8. The base material layer is a layer by the side of a thermoplastic resin layer among the said laminated structure. The results are shown in Table 2.

Example 10
A laminate and a molded article were produced in the same manner as in Example 9 except that the composition of the welding layer of the protective layer was changed to polyester-based thermoplastic elastomer 1 (80 mass%) and ABS resin 1 (20 mass%). ,evaluated. The results are shown in Table 2.

Example 11
Laminates and molded articles were produced and evaluated in the same manner as in Example 9 except that the composition of the bonding layer of the protective layer was changed to maleic acid-modified polypropylene 2 (100% by mass). The results are shown in Table 2.

Example 12
A laminate and a molded article are produced in the same manner as in Example 9 except that the composition of the bonding layer of the protective layer is changed to styrene thermoplastic elastomer 1 (70 mass%) and polypropylene 3 (30 mass%), evaluated. The results are shown in Table 2.

Example 13
Laminates and molded articles were produced and evaluated in the same manner as in Example 9 except that the composition of the welding layer of the protective layer was changed to polyester-based thermoplastic elastomer 2 (100% by mass). The results are shown in Table 2.

Example 14
Maleic acid modified polypropylene 3 (100% by mass) for the composition of the bonding layer of the protective layer, polypropylene 4 (100% for mass) for the composition of the base layer, 300 μm for the thickness of the protective layer A laminate and a molded article were produced and evaluated in the same manner as in Example 9 except that polycarbonate 1 was used. The results are shown in Table 2.

Example 15
A laminate and a molded body were manufactured and evaluated in the same manner as in Example 14 except that the resin supplied at the time of manufacturing the molded body 2 was AS resin 1. The results are shown in Table 2.

Example 16
Laminates and molded articles were produced and evaluated in the same manner as in Example 14 except that the supplied resin at the time of producing the molded article 2 was polycarbonate-ABS resin alloy 1. The results are shown in Table 2.

Example 17
Laminates and molded articles were produced and evaluated in the same manner as in Example 14 except that the resin supplied during production of the molded article 2 was changed to the polyamide-ABS resin alloy 1. The results are shown in Table 2.

Example 18
The anchor coat 1 was applied by gravure coating on one side of a 200 μm thick base layer (polypropylene 1) so that the film thickness after drying would be 100 nm. Thereafter, a welding layer (polyester-based thermoplastic elastomer 1) was extrusion laminated on the surface coated with the anchor coat of the base material layer to form a 300 μm thick three-layer protective layer (welding layer / anchor coat layer / base Material layer). Except for this, laminates and molded articles were produced and evaluated in the same manner as in Example 8. The results are shown in Table 2.

Example 19
Laminates and molded articles were produced and evaluated in the same manner as in Example 18 except that the anchor coat layer was changed to anchor coat 2. The results are shown in Table 2.

Example 20
Laminates and molded articles were produced and evaluated in the same manner as in Example 18 except that the anchor coat layer was changed to anchor coat 3. The results are shown in Table 2.

Comparative example 2
A laminate and a molded body were manufactured and evaluated in the same manner as in Example 8 except that the composition of the protective layer (welding layer) was changed to ABS resin 1 (100% by mass). The results are shown in Table 2.

Comparative example 3
The polypropylene sheet obtained in “(1) Production of a thermoplastic resin layer” in Example 8 is subjected to a corona treatment, and a urethane resin (“DIC Corporation” manufactured by DIC Corporation) is applied thereon so that the film thickness after drying becomes 230 nm. Hydran WLS-202 ") was applied by a bar coater and dried at 80 ° C. for 1 minute to form an easily bonding layer. The corona treatment was applied to the surface of the polypropylene sheet using a high frequency power source (Wedge Corporation high frequency power source "CT-0212"). On the easily bonding layer, a binder ("IMB-HF006" manufactured by Teikoku Ink Mfg. Co., Ltd.) was printed by screen printing to obtain a laminate.

The resulting laminate is attached to the mold used for the production of the molded body 2 in Example 8, and the ABS resin 1 is molded by a hydraulic injection molding machine (“IS-80 EPN” manufactured by Toshiba Machine Co., Ltd.) The mixture was supplied to the inside and integrated to produce a molded body. About the obtained molded object, the design damage and the adhesive strength were evaluated by the same method as Example 1. The results are shown in Table 2.

From Tables 1 and 2, the laminates of Examples 1 to 20 do not cause design damage when coming into contact with various molding resins, and further have sufficient adhesion strength with the molding resins, and are highly versatile. It turns out that it is a decoration sheet. Further, it can be seen from Table 2 that the laminates of Examples 8 to 20 do not undergo deformation such as warpage or distortion during molding, and have an excellent appearance even after molding.

While several embodiments and / or examples of the present invention have been described above in detail, those skilled in the art will appreciate that the exemplary embodiments and / or examples are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many modifications to the embodiment. Accordingly, many of these variations are included within the scope of the present invention.
The documents described in this specification and the contents of the application on which the Paris Convention priority of the present application is based are all incorporated.

Claims

Including a thermoplastic resin layer and a protective layer,
The protective layer comprises a weld layer,
The laminated body in which the said welding layer contains a thermoplastic elastomer.
The laminate according to claim 1, wherein the thermoplastic elastomer of the welding layer is a polyester thermoplastic elastomer.
The protective layer includes a base material layer on the thermoplastic resin layer side of the welding layer,
The base material layer contains one or more resins selected from the group consisting of polyolefin, polycarbonate, acrylic resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polystyrene, polyester and polyamide. Or the laminated body as described in 2.
The protective layer includes a bonding layer between the welding layer and the base layer,
The laminate according to claim 3, wherein the bonding layer contains one or more resins selected from the group consisting of modified polyolefins, styrenic thermoplastic elastomers, and polyolefins.
The protective layer includes an anchor coat layer between the welding layer and the base layer,
The laminate according to claim 3, wherein the anchor coat layer contains one or more resins selected from the group consisting of urethane resins, acrylic resins, polyolefins, and polyesters.
The laminate according to any one of claims 1 to 5, wherein the welding layer further contains an acrylonitrile-butadiene-styrene copolymer.
The laminate according to any one of claims 1 to 6, wherein the thermoplastic resin layer contains a polyolefin.
The laminate according to claim 7, wherein the thermoplastic resin layer comprises polypropylene.
The laminate according to claim 8, wherein an isotactic pendart fraction of the polypropylene is 85 mol% to 99 mol%.
10. The laminate according to claim 8, wherein the crystallization rate of said polypropylene at 130 ° C. is 2.5 min −1 or less.
The laminate according to any one of claims 8 to 10, wherein the polypropylene contains smectica crystals.
The laminate according to any one of claims 8 to 11, wherein the polypropylene has an exothermic peak of 1.0 J / g or more on the low temperature side of the maximum endothermic peak in a differential scanning calorimetry curve.
The laminate according to any one of claims 7 to 12, wherein the thermoplastic resin layer does not contain a nucleating agent.
The thermoplastic resin layer according to any one of claims 1 to 6, which contains one or more selected from the group consisting of polycarbonate, polyamide resin, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, and acrylic resin. Description laminate.
The laminate according to any one of claims 1 to 14, wherein a print layer is provided on a part or the whole of the surface on the protective layer side of the thermoplastic resin layer.
One or more resins selected from the group consisting of a urethane resin, an acrylic resin, a polyolefin, and a polyester, including an easy bonding layer on a part or the whole of the surface on the protective layer side of the thermoplastic resin layer The laminate according to any one of claims 1 to 15, which comprises
The surface of the easy bonding layer opposite to the thermoplastic resin layer includes an undercoat layer containing one or more resins selected from the group consisting of urethane resin, acrylic resin, polyolefin and polyester, and the undercoat layer And a metal layer containing one or more metal elements selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum and zinc on the opposite side of the easy bonding layer. The layered product according to claim 16.
A molded body produced using the laminate according to any one of claims 1 to 17.
The laminate according to any one of claims 1 to 17, and a member selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polycarbonate, polyester, polyamide, polystyrene, acrylonitrile-styrene copolymer, and acrylic resin 1 The molded object manufactured using the above resin for shaping | molding.
The molded article according to claim 18 or 19, wherein the thermoplastic resin layer in the laminate contains polypropylene, and the isotactic pendart fraction of the polypropylene is 85 mol% to 99 mol%.
The molded article according to any one of claims 18 to 20, wherein the thermoplastic resin layer in the laminate contains polypropylene, and the crystallization rate of the polypropylene at 130 ° C is 2.5 min -1 or less.
A method for producing a molded body, comprising: attaching the laminate according to any one of claims 1 to 17 to a mold and supplying a molding resin to integrate the molded resin.
A molded body, wherein the laminate according to any one of claims 1 to 17 is shaped to conform to a mold, the shaped laminate is attached to the mold, and a molding resin is supplied and integrated. Manufacturing method.
The resin for molding is at least one resin selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polycarbonate, polystyrene, polyester, polyamide, acrylonitrile-styrene copolymer, and acrylic resin. The manufacturing method of the molded object as described in-.